Biochemical
acyl
transfer
cascades,
such
as
those
initiated
by
the
adenylation
of
carboxylic
acids,
are
central
to
various
biological
processes,
including
protein
synthesis
and
fatty
acid
metabolism.
Designing
aqueous
cascades
outside
biology
remains
challenging
due
need
control
multiple,
sequential
reactions
in
a
single
pot
manage
stability
reactive
intermediates.
Herein,
we
developed
abiotic
using
aminoacyl
phosphate
esters,
synthetic
counterparts
adenylates,
drive
chemical
self-assembly
pot.
We
demonstrated
that
structural
elements
amino
side
chains
(aromatic
versus
aliphatic)
significantly
influence
reactivity
half-lives
ranging
from
hours
days.
This
behavior,
turn,
affects
number
couplings
can
achieve
network
propensity
activated
intermediate
structures.
The
constructed
bifunctional
peptide
substrates
featuring
chain
nucleophiles.
Specifically,
aromatic
acids
facilitate
formation
transient
thioesters,
which
preorganized
into
spherical
aggregates
further
couple
chimeric
assemblies
composed
esters
thioesters.
In
contrast,
aliphatic
lack
ability
form
structures,
predominantly
lead
hydrolysis,
bypassing
elongation
after
thioester
formation.
Additionally,
mixtures
containing
multiple
substrates,
achieved
selective
product
following
distinct
pathway
favors
through
self-assembly.
By
coupling
molecules
with
varying
timescales,
reaction
clocks
lifetimes
dynamics,
thereby
facilitating
precise
temporal
regulation.
Nature,
Год журнала:
2025,
Номер
637(8046), С. 594 - 600
Опубликована: Янв. 15, 2025
Abstract
Cells
display
a
range
of
mechanical
activities
generated
by
motor
proteins
powered
through
catalysis
1
.
This
raises
the
fundamental
question
how
acceleration
chemical
reaction
can
enable
energy
released
from
that
to
be
transduced
(and,
consequently,
work
done)
molecular
catalyst
2–7
Here
we
demonstrate
molecular-level
transduction
force
8
in
form
contraction
and
re-expansion
cross-linked
polymer
gel
driven
directional
rotation
artificial
catalysis-driven
9
motors.
Continuous
360°
rotor
about
stator
motor-molecules
incorporated
polymeric
framework
twists
chains
network
around
one
another.
progressively
increases
writhe
tightens
entanglements,
causing
macroscopic
approximately
70%
its
original
volume.
The
subsequent
addition
opposite
enantiomer
fuelling
system
powers
reverse
direction,
unwinding
entanglements
re-expand.
Continued
twisting
strands
new
direction
causes
re-contract.
In
actuation,
motor-molecule
produces
other
physical
outcomes,
including
changes
Young
modulus
storage
modulus—the
latter
is
proportional
increase
strand
crossings
resulting
rotation.
experimental
demonstration
against
load
synthetic
organocatalyst,
mechanism
6
,
informs
both
debate
3,5,7
surrounding
generation
biological
motors
design
principles
6,10–14
for
nanotechnology.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(30), С. 20720 - 20727
Опубликована: Июль 18, 2024
Coupling
a
photochemical
reaction
to
thermal
exchange
process
can
drive
the
latter
nonequilibrium
steady
state
(NESS)
under
photoirradiation.
Typically,
systems
use
separate
motifs
for
photoresponse
and
equilibrium-related
processes.
Here,
we
show
that
photoswitchable
imines
fulfill
both
roles
simultaneously,
autonomously
driving
dynamic
covalent
system
into
NESS
continuous
light
irradiation.
We
demonstrate
this
using
transimination
reactions,
where
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
Continuous
directionally
biased
360°
rotation
about
a
covalent
single
bond
was
recently
realized
in
the
form
of
chemically
fueled
1-phenylpyrrole
2,2′-dicarboxylic
acid
rotary
molecular
motor.
However,
original
fueling
system
and
reaction
conditions
resulted
motor
directionality
only
∼3:1
(i.e.,
on
average
backward
for
every
three
forward
rotations),
along
with
catalytic
efficiency
operation
97%
fuel
14%.
Here,
we
report
efficacy
series
chiral
carbodiimide
fuels
hydrolysis
promoters
(pyridine
pyridine
N-oxide
derivatives)
driving
improved
directional
this
motor-molecule.
We
outline
complete
network
operation,
composed
directional,
futile,
slip
cycles.
Using
derivatives
where
final
conformational
step
is
either
very
slow
or
completely
blocked,
phenylpyrrole
diacid
becomes
enantiomerically
enriched,
allowing
kinetic
gating
individual
steps
cycle
to
be
measured.
The
that
produces
highest
gives
13%
enantiomeric
excess
(e.e.)
anhydride-forming
kinetically
gated
step,
while
most
effective
promoter
generates
90%
e.e.
step.
Combining
best-performing
into
results
92%
e.e..
Under
dilute
chemostated
regime
(to
avoid
N-acyl
urea
formation
at
high
concentrations
promoters),
continuously
rotates
∼24:1
24
rotations)
>99%
51%.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(13), С. 1827 - 1838
Опубликована: Июнь 21, 2024
ConspectusChemists
have
long
been
inspired
by
biological
photosynthesis,
wherein
a
series
of
excited-state
electron
transfer
(ET)
events
facilitate
the
conversion
low
energy
starting
materials
such
as
H
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 11, 2025
The
modulation
of
molecular
recognition
underpins
numerous
wide-ranging
applications
and
has
inspired
the
development
a
myriad
switchable
receptors,
in
particular
photo-
or
redox-responsive
hosts.
Herein,
we
report
highly
versatile
three-state
cation
receptor
family
switch
system
based
on
an
overcrowded
alkene
strapped
with
crown
ethers,
which
can
be
switched
by
both
redox
light
stimuli,
thereby
combining
advantages
approaches.
Specifically,
neutral
switches
quantitatively
converted
between
anti-
syn-folded
geometries
irradiation,
leading
to
discovery
significant
increase
decrease
binding
affinity,
was
exploited
shuttle
pseudorotaxane-forming
dibenzylammonium
guest
ethers
slightly
different
sizes.
Alternatively,
two-electron
oxidation
orthogonal,
dicationic,
nonvolatile
state
completely
turns
off
host,
ejecting
guest.
Upon
reduction,
metastable
is
first
formed,
then
thermally
relaxes,
resulting
unique,
autonomous,
cation-dependent
multistate
switching
cascade.
